Well Ordered Polymer Melts from Blends of Disordered Triblock Copolymer Surfactants and Functional Homopolymers

Microphase segregated block copolymer melts and solids have long garnered significant scientific interest due to their ability to spontaneously form periodic morphologies at controllable length scales. Their utility as stand-alone nanostructured functional materials or as templates for the fabrication of hierarchical solids is well documented. However, their deployment in large scale applications has often been limited by the cost and scalability of the living polymerization techniques necessary for the precise control of molecular parameters required to achieve well defined morphologies. Here, we report that well ordered, processible, and functional polymer melts with periodic nanostructures can be obtained in bulk quantity by simple blending of commercially available triblock copolymer surfactants with a series of commodity homopolymers that selectively associate with one of blocks through hydrogen bonding. While the neat surfactants are disordered in the melt, scattering measurements indicate that the blends undergo a disorder-to-order transition to yield stable microphase separated structures. Moreover, the functional groups present in the homopolymers provide a convenient handle for subsequent templating schemes including phase selective chemistries and depositions, chemical modifications, and binding of active dopants including nanoparticles. The results are general, and suggest a low cost, high volume strategy to produce ordered spherical, cylindrical, or lamellar microphase separated polymer melts for commercial use. The microphase segregation of block copolymers is governed thermodynamically by the product of Flory–Huggins interaction parameter (x) of the copolymer segments and the total number of monomers per copolymer chain (N). Since the molecular interactions for a given copolymer are dictated by their chemical structure, the segregation strength